The Role of Lignin Molecular Weight on Activated Carbon Pore Structure.

Over the past decade, the production of biofuels from lignocellulosic biomass has steadily increased to offset the use of fuels from petroleum. To make biofuels cost-competitive, however, it is necessary to add value to the "ligno-" components (up to 30% by mass) of the biomass. The properties of lignin, in terms of molecular weight (MW), chemical functionality, and mineral impurities often vary from biomass source and biorefinery process, resulting in a challenging precursor for product development.

Purification and Fractionation of Lignin via ALPHA: Liquid-Liquid Equilibrium for the Lignin-Acetic Acid-Water System.

In order to effectively practice the Aqueous Lignin Purification with Hot Agents (ALPHA) process for lignin purification and fractionation, the temperatures and feed compositions where regions of liquid-liquid equilibrium (LLE) exist must be identified. To this end, pseudo-ternary phase diagrams for the lignin-acetic acid-water system were mapped out at 45-95 °C and various solvent: feed lignin mass ratios (S : F). For a given temperature, the accompanying SL (solid-liquid), SLL (solid-liquid-liquid), and one-phase regions were also located.

Carbon fibers derived from liquefied and fractionated poplar lignins: The effect of molecular weight.

Lignin recovered from poplar, a key woody biomass resource proposed for lignocellulosic refineries, was investigated for conversion into carbon fibers. Aqueous solutions of ethanol at selected temperatures and compositions, where the requisite solvent and liquefied-lignin phases form, were used to purify and fractionate hybrid poplar (HP) lignin using the Aqueous Lignin Purification with Hot Agents (ALPHA) process. Sugars (<0.

Fractionating and Purifying Softwood Kraft Lignin with Aqueous Renewable Solvents: Liquid-Liquid Equilibrium for the Lignin-Ethanol-Water System.

Hot ethanol-water solutions can be used to simultaneously fractionate and purify softwood Kraft lignin through the Aqueous Lignin Purification with Hot Agents (ALPHA) process, using the regions of liquid-liquid equilibrium (LLE) that form at selected temperatures and solvent-to-lignin feed (S/F) ratios. Lignin, ethanol, and water compositions are measured for the solvent-rich (SR) and lignin-rich (LR) liquid phases in mutual equilibrium, as well as the lignin and metals mass distributions between the two phases. As depicted in quasi-ternary diagrams for clarity, both temperature and S/F ratio can be used to grow, merge, and even split the regions of LLE, giving significant control over both molecular weight (MW) and lignin purity.

Solvated liquid-lignin fractions from a Kraft black liquor.

A softwood Kraft black liquor was acidified with carbon dioxide at 115°C and 6.2 bar over a pH range of 13.6-9.

Quantitative analysis of polydisperse systems via solvent-free matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

Quantitative analysis of partially soluble and insoluble polydisperse materials is challenging due to the lack of both appropriate standards and reliable analytical techniques. To this end, matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) incorporating a solvent-free sample preparation technique was investigated for the quantitative analysis of partially soluble, polydisperse, polycyclic aromatic hydrocarbon (PAH) oligomers. Molecular weight standards consisting of narrow molecular weight dimer and trimer oligomers of the starting M-50 petroleum pitch were produced using both dense-gas/supercritical extraction (DGE/SCE) and preparative-scale, gel permeation chromatography (GPC).

The effects of molecular weight distribution and sample preparation on matrix-assisted laser desorption/ionization time-of-flight mass spectrometric analysis of petroleum macromolecules.

To date there have been no systematic, quantitative investigations of the effect of sample preparation on the matrix-assisted laser desorption/ionization time-of-flight (MALDI) mass spectrometry response for polydisperse systems. To this end, the interrelationships between sample preparation, analyte molecular weight distribution (MWD) and solubility, and signal response were investigated for mixtures of alkylated polycyclic aromatic hydrocarbon (PAH) oligomers, the constituents of petroleum pitch that serve as precursors for advanced carbon materials. These PAH oligomers served as a useful analyte system for study, as their solvent solubilities decrease significantly with each increasing oligomeric unit.

Design and evaluation of nonfluorous CO2-soluble oligomers and polymers.

Ab initio molecular modeling is used to design nonfluorous polymers that are potentially soluble in liquid CO2. We have used calculations to design three nonfluorous compounds meant to model the monomeric repeat units of polymers that exhibit multiple favorable binding sites for CO2. These compounds are methoxy isopropyl acetate, 2-methoxy ethoxy-propane, and 2-methoxy methoxy-propane.

The formation of fluorinated tetraphenylporphyrin nanoparticles via rapid expansion processes: RESS vs RESOLV.

Organic nanoparticles of a fluorinated tetraphenylporphyrin (TBTPP) were produced by rapid expansion of supercritical CO(2) solutions into both air (RESS) and an aqueous receiving solution containing a stabilizing agent (RESOLV). The effect of processing conditions on both particle size and form was investigated. The size of the porphyrin nanoparticles produced via RESS increased in a well-behaved manner from 40 to 80 nm as the preexpansion temperature increased from 40 to 100 degrees C, independent of porphyrin concentration, degree of saturation, and preexpansion pressure.

Supercritical water oxidation of the PCB congener 2-chlorobiphenyl in methanol solutions: a kinetic analysis.

Incineration is commonly used to destroy polychlorinated biphenyl (PCB) wastes, but this method of treatment is not ideal for all mixed liquid wastes, especially those containing radioactive materials. Therefore, other remediation technologies are needed to efficiently treat these waste forms. This study examined the supercritical water oxidation (SCWO) of 2-chlorobiphenyl (2-PCB), using hydrogen peroxide as the oxidant and methanol as a cosolvent at 2 vol %.

RESS for the preparation of fluorinated porphyrin nanoparticles.

Rapid Expansion of Supercritical Solutions (RESS) was used to produce clean, surfactant-free nanoparticles (average size = 60 nm) of a fluorinated tetraphenylporphyrin from supercritical solutions with CO2.